Biocidally-active, 1,3-benzodithiole-2-one and 1,3-benzodithiole-2-thione compounds

ABSTRACT

1,3-Benzodithiole-2-one and 1,3-benzodithiole-2-thione compounds are disclosed including the novel method of preparing said compounds and their biocidal activity.

CROSS REFERENCE TO RELATED APPLICATION

This application is a division of application Ser. No. 618,255, filedSept. 30, 1975, now U.S. Pat. No. 4,084,954, issued Apr. 18, 1978.

BACKGROUND OF THE INVENTION

This invention relates generally to new and useful biocidally activecompounds. More specifically, it relates to novel1,3-benzodithiole-2-one and 1,3-benzodithiole-2-thione compoundsprepared by an unusual but highly simple and convenient cyclizationreaction. In fact, it is due to this synthesis that the numerousderivatives disclosed herein can be obtained so easily and in goodyields.

The novel compounds of this invention are useful in treating pestsassociated with growing plants in order to beneficially enhance thegrowth and/or yield-potential of said growing plants. This isaccomplished by applying a biocidally active amount of the subjectcompound to soil, seed or the growing plant. The term "pests" as usedherein is meant to include plant pests such as weeds and fungi, andanimal pests such as arachnids, nematodes, or insects.

The concentration, rate and physical form of the administered compoundare determined by the particular application, said applicationcomprising one or more of the following:

(1) herbicidal

(2) fungicidal

(3) acaricidal

(4) nematocidal

(5) insecticidal

Generally, for each particular application, there will be a preferredrange with respect to concentration, a preferred amount with respect torate and a preferred type with respect to formulation.

For purposes of this disclosure and for the sake of convenience andclarity, certain terms used herein are defined as follows:

The phrase "treating pests associated with growing plants" signifies theapplication of a compound as herein defined to pests associated withgrowing plants which embraces germinating plants, e.g. seeds, sprouts,seedlings, and fully grown plants. The mode of application will dependon the desired end use. For example, if the treatment is forpre-emergent herbicidal use, the compound will be administered into thesoil which contains the growing seeds. In contrast, when used as apost-emergent herbicide, the compound will be applied to the growingplants after seeds have germinated.

When treatment comprises foliar fungicidal application, the compound isadministered, as a spray, directly onto the leaves and other aboveground portions of diseased plants.

For use as an acaricide, the compound may be applied by contacting theleaves (or plant) directly or as a soil incorporation in the soil wherethe plant is growing.

For use as a soil or seed treatment fungicide, the compound is usuallyapplied as a seed treatment, or as a drench and/or incorporation to thesoil containing the seed or the growing plant.

For use as a nematocide, the compound is normally applied directly as adrench and/or incorporation to the soil containing the growing plant.

For use as an insecticide, the compound is usually applied topically tothe above ground portions of infested plants and/or to the soilcontaining the growing plants.

All of the aforesaid treatments, whatever the objective, have a unitaryresult. That is, they beneficially enhance or improve the growth and/oryield potential of the treated plant.

The term "biocidally active amount" means an amount of compound whicheffectively permits the desired objective.

SUMMARY OF THE INVENTION

Accordingly, this invention is concerned with ##STR1## wherein W is O orS; Y is selected from hydrogen, cyano, alkylsulfonyl, nitro andtrifluoromethyl; X is selected from alkyl and alkenyl of up to 6 carbonatoms, nitro, trichloromethyl, trifluoromethyl, trifluoromethoxy,trifluoromethylthio, trifluoromethylsulfoxyl, trifluoromethylsulfonyl,methoxymethyl, cyano, carboxy, carbamyl, halogen (F, Cl, Br, I),hydroxy, acetylamino, amino, N-phenylamino, N,N-diallylamino, alkoxy,N-morpholino, N-piperidino, N-piperazino, N-pyrrolidino,dimethylaminodithiocarbamyl, carboalkoxy, alkylthio, mono- anddi-alkylamino, N-alkylcarbamyl, N,N-dialkylcarbamyl, alkylsulfoxy,alkylsulfonyl, said alkyl groups containing from 1 to 4 carbon atoms; nis an integer from 0 to 3; and salts thereof.

Of particular interest are compounds as shown above wherein W is 0, Y isnitro and n is 1, such as:

6-methyl-4-nitro-1,3-benzodithiole-2-one

4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-one

4,6-dinitro-1,3-benzodithiole-2-one

6-fluoro-4-nitro-1,3-benzodithiole-2-one

6-chloro-4-nitro-1,3-benzodithiole-2-one

6-cyano-4-nitro-1,3-benzodithiole-2-one.

Other preferred compounds include those as shown above wherein W is Q, Yis nitro and n is 2 such as:

6-chloro-7-methyl-4-nitro-1,3-benzodithiole-2-one

7-dimethylaminodithiocarbamyl-4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-one

7-chloro-4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-one.

Still others which are preferred as those as shown above wherein W is Q,Y is nitro and n is 3 such as:

5,7-dimethyl-4,6-dinitro-1,3-benzodithiole-2-one.

Another compound which is preferred as shown above wherein W is O, Y isnitro and n is 0 is:

4-nitro-1,3-benzodithiole-2-one.

Still others which are preferred are those as shown above wherein W isO, Y is trifluoromethyl and n is 1 such as:

6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one.

Still others which are preferred are those as shown above wherein W isO, Y is trifluoromethyl and n is 2 such as:

7-di-n-propylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

7-monoisopropylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

7-mono-n-propylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

7-diethylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

7-n-propylthio-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

7-isopropylthio-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

7-diallylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

7-methylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

7-monobutylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

7-dibutylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

7-monophenylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

6-nitro-7-piperidino-4-trifluoromethyl-1,3-benzodithiole-2-one

7-morpholino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

6-nitro-7-pyrrolidino-4-trifluoromethyl-1,3-benzodithiole-2-one.

Still others which are preferred are those as shown above wherein W isO, Y is trifluoromethyl and n is 3.

Still others which are preferred are those as shown above wherein W isS, Y is nitro and n is 1 such as:

4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-thione

6-methyl-4-nitro-1,3-benzodithiole-2-thione.

Still others which are preferred are those as shown above wherein W isO, Y is hydrogen and n is 1 such as:

5-nitro-1,3-benzodithiole-2-one

5-trifluoromethyl-1,3-benzodithiole-2-one.

Also within the purview of this invention is the novel process forpreparing such compounds involving a unique cyclization step as well asthe use of such compounds to beneficially enhance the growth and/oryield-potential of plants.

DETAILED DESCRIPTION OF THE INVENTION

The novel compounds of this invention are prepared by a novel procedurewherein a unique cyclization step is involved. It is this syntheticmethod which allows for the formation of the numerous compoundsdisclosed herein. Compounds which would ordinarily be inaccessible or atbest, tedious and difficult to make, are rendered available by anunusually simple and mild synthesis.

The process can be expressed by the following reactions: ##STR2##wherein Y is selected from hydrogen, cyano, alkylsulfonyl, nitro andtrifluoromethyl; X is selected from alkyl and alkenyl of up to 6 carbonatoms, nitro, trichloromethyl, trifluoromethyl, trifluoromethoxy,trifluoromethylthio, trifluoromethylsulfoxyl, trifluoromethylsulfonyl,methoxymethyl, cyano, carboxy, carbamyl, halogen (F, Cl, Br, I),hydroxy, acetylamino, amino, N-phenylamino, N,N-diallylamino, alkoxy,N-morpholino, N-piperidino, N-piperazino, N-pyrrolidino,dimethylaminodithiocarbamyl, carboalkoxy, alkylthio, mono- anddialkylamino, N-alkylcarbamyl, N,N-dialkylcarbamyl, alkylsulfoxy,alkylsulfonyl, said alkyl groups containing from 1 to 4 carbon atoms andn is an integer from 0 to 3; Z is halogen (F, Cl, Br, I) or alkoxy, andR and R' are each alkyl groups, straight- or branch-chained, containingfrom 1 to 4 carbon atoms.

Starting material A is typically a halobenzene derivative, many of whichare commercially available. If not, one can easily synthesize thedesired compound using well-documented chemical techniques. As isapparent, the halo group (Z) and the adjacent nitro group both undergosubstitution thereby effecting cyclization to form the heterocyclic5-membered ring. The other reagent, B, is an N,N-dialkyldithiocarbamicacid or acid salt, such as the sodium salt.

The attractiveness of the above process is that under relatively mildconditions, using generally available or easily accessible reagents andin a single step, one can obtain the desired compounds in good yields.The intermediate product C of this reaction can in many preparations beisolated. In others it undergoes the cyclization reaction, even at lowtemperatures, to produce final product D, the substituted1,3-benzodithiole-2-ones.

The novelty of this synthetic method is clearly evident to one skilledin the art. It enables one to fuse onto a benzene ring containingadjacent nitro and halo groups a cyclic ring having the structure:##STR3##

Importantly, it allows one to do this under mild conditions and usingvarious chlorobenzene derivatives so that almost any desired substitutedcompound results.

The reaction process is carried out in the temperature range of from 0°C. to 200° C. In many instances, the reaction proceeds at roomtemperature or lower, whereas, in some cases, elevated temperatures maybe desired in order to accelerate the reaction.

The reaction is usually carried out in a solvent, although the solventmay be omitted if effective dissolution of materials is possible. Asolvent is generally preferred, however, and it can be any solvent whichdoes not enter into the reaction and in which the reactants are solubleto some extent. Suitable solvents are dimethylformamide,dimethylsulfoxide, acetone and methyl isobutyl ketone.

The mole ratio of reagents A and B is normally 1 to 1, however, it isgenerally preferred to use a slight excess of reagent B to ensure morecomplete reaction.

A co-product E is usually formed during the formation of desired productD. This co-product is easily separated from product D using solventdifferential properties. It is converted to compound D by treatmentunder basic conditions, such as sodium hydroxide in an aqueous solutionor suspension containing solvent. A typical solvent for such conversionis dimethylsulfoxide.

The reaction is carried out at temperatures ranging from 0° to 200° C.The work-up is standard--product is obtained by precipitation, washing,drying and recrystallization if necessary.

The 1,3-benzodithiole-2-thione compounds disclosed herein are obtainedby conversion of the corresponding 1,3-benzodithiole-2-one compounds.The conversion of >C═O to >C═S is well-known in the chemical literatureand several ways are available for effecting it.

One way uses disodium trithiocarbonate as the sulfurizing agent. Othersuitable reagents include sodium hydrosulfide and potassium thiocyanate.

The biocidal processes of this invention comprise applying a biocidallyeffective amount of a compound disclosed herein to soil, seed or growingplant. The compounds are formulated for use either as sprays made up byadding water to emulsifiable concentrates or wettable powders, asgranules or as dispersions on carriers such as attapulgite claygranules, peat moss, fertilizer, vermiculite, etc. The compounds arequite insoluble in water, and hence, for the preparation of emulsions orwettable powders, the compounds are preferably formulated with wettingagents.

Since numerous compounds disclosed herein are free bases and acids, theycan be converted to acid salts (free bases) and base salts (free acids).

The acid-addition and base-addition salts are within the purview of thisinvention. The acid-addition salts are easily prepared by treating theamine base with a substantially equimolar amount of a chosen acid in anaqueous solution or in a suitable organic solvent such as methanol orethanol. The only restriction on the acid used is that it providesacceptable ions, i.e., those which do not deleteriously affect thegrowing plants. The base-addition salts are prepared in a similar mannerexcept that base instead of acid is added. The same restriction withrespect to acceptable ions applies.

For herbicidal use, the compounds disclosed herein are applied at a rateof from 0.5 lbs a.i./acre to 8.0 lbs a.i./acre.

For soil fungicidal use, the compounds disclosed herein are applied at arate of from 0.25 to 40.0 lbs a.i./acre.

For seed treatment fungicidal use the compounds disclosed herein areapplied at a rate of from 2.0 to 10.0 ounces per 100 lbs. of crop seed.

For foliar fungicidal use, the compounds disclosed herein are applied ata rate of about 200 parts per million in a suitable solvent, such aswater.

For acaricidal use, the compounds disclosed herein are applied at a rateof from 30 to 1000 parts per million in a suitable solvent, such aswater.

For nematocidal use, the compounds disclosed herein are applied at arate of from 15 to 20 parts per million in a suitable solvent, such aswater.

For insecticidal use, the compounds disclosed herein are applied at arate of from 0.2% to 10.0% in a suitable solvent, such as water.

EXAMPLE I 4-Nitro-6-trifluoromethyl-1,3-benzodithiole-2-one

To a magnetically stirred solution of2,6-dinitro-4-trifluoromethyl-chlorobenzene (445 g., 1.65 M) in acetone(3300 ml.) was added N,N-dimethyldithiocarbamic acid sodium saltdihydrate (295 g., 1.65 M) and the reaction mixture was maintained at0°-5° C. during addition.

After addition, the reaction mixture was stirred at 5°-10° C. for 90minutes and thereafter for 18 hours at room temperature.

The acetone-insoluble solids were suction filtered, washed well withwater, dried and soxhlet-extracted with hexane overnight. The hexaneextract was stripped free of solvent on a rotary evaporator under vacuumyielding 6.5 g. of desired product. A co-product (223.4 g., M.P.222°-224° C.) remained unextracted.

The acetone filtrate was stripped free of solvent under vacuum and theresidual solid washed with ethanol (100 ml.) and suction filtered. Thesolid was soxhlet extracted with hexane overnight. Removal of solventfrom the hexane extract yielded the desired product (188.5 g., 40.7%theory, M.P. 110°-111° C.).

EXAMPLE II Conversion of the co-product of Example I to4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-one

To a stirred suspension of the co-product from Example I (3.26 g.) indimethylsulfoxide (30 ml.) was added a solution of NaOH (0.88 g., 0.022M) dimethylsulfoxide (15 ml.) and water (5 ml.). The reaction mixturewas allowed to stir at room temperature under nitrogen gas for 22 hours.

The resulting solution was poured into water (300 ml.), made acidic byaddition of conc. HCl, solid filtered off, washed with water and dried.Recrystallization from hot hexane yielded pure4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-one. (Confirmed by mixedM.P. and I.R. spectra).

EXAMPLE III Conversion of4-Nitro-6-trifluoromethyl-1,3-benzodithiole-2-one to4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-thione

To a stirred and cooled solution of4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-one (14.05 g., 0.05 M) inDMSO (150 ml.) was added dropwise a solution of disodiumtrithiocarbonate (48.15 g., 0.12 M of 40% aqueous solution). Thereaction mixture was permitted to stir for 60 minutes at about 15° C.and thereafter for 21/2 hours at ambient temperatures.

The resulting solution was poured into an excess of water, acidifed andextracted with chloroform (3×100 ml.). The organic layer was separated,dried, stripped free of solvent and chromatographed over silica gel.Elution with hexane removes elemental sulfur. Another elution withhexane yields the desired product. (4.5 g., 30.3% theory, M.P.109.5°-110.5° C.).

EXAMPLE IV

The procedure of Example I is repeated wherein the followingchlorobenzene derivatives are used in place of2-6-dinitro-4-trifluoromethylchlorobenzene to provide the correspondingproducts:

    ______________________________________                                        chlorobenzene derivative                                                                       Product                                                      ______________________________________                                        2,6-dinitro-4-methyl-chloro-                                                                   6-methyl-4-nitro-1,3-benzodi-                                benzene          thiole-2-one                                                                  M.P. 163°-164° C.                              2,4,6-trinitro-chlorobenzene                                                                   4,6-dinitro-1,3-benzodithiole-                                                2-one                                                                         M.P. 129°-131° C.                              2,6-dinitro-4-fluoro-chloro-                                                                   6-fluoro-4-nitro-1,3-benzodi-                                benzene          thiole-2-one                                                                  M.P. 98°-100° C.                               4-chloro-2,6-dinitro-chloro-                                                                   6-chloro-4-nitro-1,3-benzodi-                                benzene          thiole-2-one                                                                  M.P. 152°-153° C.                              1,4-dichloro-3-methyl-2,6-                                                                     6-chloro-7-methyl-4-nitro-1,3-                               dinitro-chlorobenzene                                                                          benzodithiole-2-one                                                           M.P. 147°-148° C.                              3-chloro-2,6-dinitro-4-                                                                        7-dimethylaminodithiocarbamyl-                               trifluoromethylchlorobenzene                                                                   4-nitro-6-trifluoromethyl-1,3-                                                benzodithiole-2-one                                                           M.P. 138°-141° C.                              3-chloro-2,6-dinitro-4-                                                                        7-chloro-4-nitro-6-trifluoro-                                trifluoromethylchlorobenzene                                                                   methyl-1,3-benzodithiole-2-one                                                M.P. 87°-89° C.                                2,6-dinitrochlorobenzene                                                                       4-nitro-1,3-benzodithiole-2-one                                               M.P. 110°-111° C.                              3,5-dimethyl-2,4,6-trinitro-                                                                   5,7-dimethyl-4,6-dinitro-1,3-                                chlorobenzene    benzodithiole-2-one                                                           M.P. 130°-131° C.                              2,4-dinitro-6-trifluoromethyl-                                                                 6-nitro-4-trifluoromethyl-1,3-                               chlorobenzene    benzodithiole-2-one                                                           M.P. 117°-118.5° C.                            3-di-n-propylamino-2,4-                                                                        7-di-n-propylamino-6-nitro-4-                                dinitro-6-trifluoromethyl-                                                                     trifluoromethyl-1,3-benzodi-                                 chlorobenzene    thiole-2-one                                                                  M.P. 60°-61° C.                                2,4-dinitro-3-monoisopropyl-                                                                   7-monoisopropylamino-6-nitro-                                amino-6-trifluoromethyl-                                                                       4-trifluoromethyl-1,3-benzo-                                 chlorobenzene    dithiole-2-one                                                                M.P. 71.5°-72.5° C.                            2,4-dinitro-3-mono-n-propyl-                                                                   7-monopropylamino-6-nitro-4-                                 amino-6-trifluoromethyl-                                                                       trifluoromethyl-1,3-benzodi-                                 chlorobenzene    thiole-2-one                                                 3-diethylamino-2,4-dinitro-                                                                    7-diethylamino-6-nitro-4-tri-                                6-trifluoromethylchloro-                                                                       fluoromethyl-1,3-benzodithiole                               benzene                                                                       2-one                                                                                          M.P. 61°-63° C.                                2,4-dinitro-3-n-propylthio-                                                                    6-nitro-7-n-propylthio-4-tri-                                6-trifluoromethylchloro-                                                                       fluoromethyl-1,3-benzodithiole                               benzene                                                                       2-one                                                                                          M.P. 90°-91° C.                                2,4-dinitro-3-isopropylthio-                                                                   7-isopropylthio-6-nitro-4-                                   6-trifluoromethylchloro-                                                                       trifluoromethyl-1,3-benzodi-                                 benzene          thiole-2-one                                                                  M.P. 79.5°-80.5° C.                            4-cyano-2,6-dinitrochloro-                                                                     6-cyano-4-nitro-1,3-benzodi-                                 benzene          thiole-2-one                                                                  M.P. 173°-175° C.                              3-diallylamino-2,4-dinitro-6-                                                                  7-diallylamino-6-nitro-4-                                    trifluoromethylchlorobenzene                                                                   trifluoromethyl-1,3-benzodi-                                                  thiole-2-one                                                                  a liquid                                                     2,4-dinitro-3-methylamino-6-                                                                   7-methylamino-6-nitro-4-                                     trifluoromethylchlorobenzene                                                                   trifluoromethyl-1,3-benzodi-                                                  thiole-2-one                                                                  M.P. 171°-173° C.                              2,4-dinitro-3-monobutylamino-                                                                  7-mono-n-butylamino-6-nitro-                                 6-trifluoromethylchloro-                                                                       4-trifluoromethyl-1,3-benzo-                                 benzene          dithiole-2-one                                                                a liquid                                                     3-dibutylamino-2,4-dinitro-6-                                                                  7-di-n-butylamino-6-nitro-4-                                 trifluoromethylchlorobenzene                                                                   trifluoromethyl-1,3-benzo-                                                    dithiole-2-one                                                                a liquid                                                     2,4-dinitro-3-monophenylamino-                                                                 7-monophenylamino-6-nitro-4-                                 6-trifluoromethylchloro-                                                                       trifluoromethyl-1,3-benzo-                                   benzene          dithiole-2-one                                                                M.P. 121°-122° C.                              2,4-dinitro-3-piperidino-6-                                                                    6-nitro-7-piperidino-4-                                      trifluoromethylchlorobenzene                                                                   trifluoromethyl-1,3-benzo-                                                    dithiole-2-one                                                                M.P. 155°-157° C.                              2,4-dinitro-3-morpholino-6-                                                                    7-morpholino-6-nitro-4-                                      trifluoromethylchlorobenzene                                                                   trifluoromethyl-1,3-benzo-                                                    dithiole-2-one                                                                M.P. 178°-180° C.                              2,4-dinitro-3-pyrrolidino-6-                                                                   6-nitro-7-pyrrolidino-4-                                     trifluoromethylchlorobenzene                                                                   trifluoromethyl-1,3-benzodi-                                                  thiole-2-one                                                                  M.P. 104°-105° C.                              2,4-dinitrochlorobenzene                                                                       5-nitro-1,3-benzodithiole-                                                    2-one                                                                         M.P. 131°-136° C.                              2-nitro-4-trifluoromethyl-                                                                     5-trifluoromethyl-1,3-benzo-                                 chlorobenzene    dithiole-2-one                                                                M.P. 36°-42° C.                                ______________________________________                                    

EXAMPLE V

The compounds enumerated in Example IV are converted to thecorresponding 1,3-benzodithiole-2-thiones in accordance with theprocedure outlined in Example III.

EXAMPLE VI

The procedure of Example I is repeated wherein the followingN,N-dialkyldithiocarbamic acid compounds in stoichiometric equivalentamounts are used in place of N,N-dimethyldithiocarbamic acid sodium saltdihydrate with comparable results:

N,N-dimethyldithiocarbamic acid potassium salt

N,N-diethyldithiocarbamic acid sodium salt

N,N-diisopropyldithiocarbamic acid sodium salt

N,N-dibutyldithiocarbamic acid sodium salt

N-ethyl-N-methyldithiocarbamic acid sodium salt

EXAMPLE VII

The procedure of Example I is repeated wherein the following solventsare used in place of acetone with comparable results:

dimethylsulfoxide

dimethylformamide

methylisobutyl ketone

EXAMPLE VIII

The compound of Example I is prepared in the following manner: To amagnetically stirred solution of 16.2 g (60 mmoles)2,6-dinitro-4-trifluoromethylchlorobenzene in 60 ml. dimethylsulfoxidewas added dropwise a solution of 10.74 g (60 mmoles) sodiumdimethyldithiocarbamic acid. The reaction is mildly exothermic andaccompanied by evolution of oxides of nitrogen. After allowing thereaction mixture to stir for 3 hours, 450 ml. water and 225 ml.chloroform are added and, after shaking well in an extraction funnel,the chloroform extract was withdrawn and the aqueous phase similarlyextracted with two more 220 ml. portions of chloroform. The combinedchloroform extract was washed thrice with 750 ml. portions of water, anddried over anhy. Na₂ SO₄. After removing the solvent on a rotaryevaporator, the residue was chromatographed over 180 g Silica-Gel.Elution with hexane-benzene (1:1) yielded 7.3 g (43.3%)4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-one, m.p. 103°-107° C. Onerecrystallization from ethanol yielded product, m.p. 111°-112° C.

Elemental Analyses: % Found: C=33.9; H=0.9; N=4.9. % Calc: C=34.2;H=0.71; N=5.0.

NMR (CDCl₃): 8.16 δ (1H, m); 8.6 δ (1H, m).

EXAMPLE IX

The procedure of Example VIII is repeated wherein the followinghalobenzene derivatives are used in place of2,6-dinitro-4-trifluoromethylchlorobenzene to provide correspondingproducts: ##STR4##

    ______________________________________                                        halobenzene derivative                                                        Z      Y         X.sub.1    X.sub.2   X.sub.3                                 ______________________________________                                        Cl     NO.sub.2  allyl      H         H                                       Br     NO.sub.2  hexyl      H         H                                       F      NO.sub.2  H          CCl.sub.3 H                                       Cl     NO.sub.2  H          CF.sub.3 O                                                                              H                                       Cl     CF.sub.3  H          CH.sub.3 SO.sub.2                                                                       H                                       Cl     NO.sub.2  H          CF.sub.3 S                                                                              H                                       Cl     NO.sub.2  H          CF.sub.3 SO                                                                             H                                       Cl     NO.sub.2  H          CN        H                                       Cl     NO.sub.2  H          CF.sub.3 SO.sub.2                                                                       H                                       Cl     NO.sub.2  H          H         H                                       Cl     NO.sub.2  H          CH.sub.3 OCH.sub.2                                                                      H                                       Cl     CF.sub.3  H          CN        H                                       Cl     CF.sub.3  H          COOH      H                                       Cl     CF.sub.3  H          OH        H                                       Cl     CF.sub.3  H          NH.sub.2  H                                       ______________________________________                                    

EXAMPLE X

For determination of herbicidal activity for the herein disclosedcompounds, the following screen was used: The candidate compound isapplied at 8 lb/A in 40 gal/ A to one foot square flats containing seedsor plants of the test plant species. Visual ratings of phytotoxicity aremade after 7 and 14 days. The phytotoxicity rating system is based on0=no control and 10=complete kill or 100% control.

For post emergent use, the flats are planted with the desired plantspecies 7-9 days prior to spraying. By spraying time a well establishedflat of plants is ready for spraying. For incorporated pre-emergenceuse, the flats are prepared and planted with seed of the variousspecies. A sheet of plastic is then placed over the seed and a measuredquantity of screened soil normally used for covering the seed is placedon top. The flat is then ready for spraying. After spraying, the soil ontop of the sheet of plastic is mixed thoroughly and spread evenly overthe surface of the flat.

The plant species used in herebicide screening are corn (Zea mays L.),wheat (Triticum avesticum L.), cotton (Gossypium hirsutum L), soybeans(Glycine mx L.), barnyardgrass (Echinochloa crusgalli L. Beauv), foxtail(Setaria viridis L. Beauv), morningglory (Ipomea purpurea L. Roth), andpigweed (Amaranthus retroflexus L.).

The following compounds exhibited herbicidal properties:

7-di-n-propylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

7-diethylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

7-diallylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

EXAMPLE XI

For determination of soil fungicidal activity for the herein disclosedcompounds, the following screen was used: Two potato-dextrose-agarplates of the desired fungal organism are blended in a Waring blenderwith 50 mls of sterile water. The resulting mixture is added to 3000 gof sterile soil in a plastic bag and thoroughly blended. Cucumber seedsare planted in 4 oz. cups containing a measured amount of the inoculatedsoil mixture. Finally, 10 mls of the candidate compound at 40 lb/A isatomized as a drench over the prepared soil. After 14 days evaluationsare made based on the number of surviving seedlings in the treated cupcompared to the untreated check.

The organisms used in the primary soil fungicide screen are Rhizoctoniasolani and Pythium ultimum.

The following compounds exhibited soil fungicidal properties:

4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-one

4-nitro-1,3-benzodithiole-2-one

6-fluoro-4-nitro-1,3-benzodithiole-2-one

7-chloro-4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-one

7-monoisopropylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

7-mono-n-propylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

7-diethylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

7-methylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

6-nitro-7-piperidino-4-trifluoromethyl-1,3-benzodithiole-2-one

7-n-propylthio-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

7-isoipropylthio-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-thione

7-dimethylaminodithiocarbamyl-4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-one

5-trifluoromethyl-1,3-benzodithiole-2-one

1,3-benzodithiole-2-one

1,3-benzodithiole-2-thione

EXAMPLE XII

For determination of foliar fungicidal activity for the herein disclosedcompounds, the following screen was used. The candidate compound isapplied at 200 ppm to Bonny Best variety of tomato plants which have 2-4true leaves. The treated plants are held at a relative humidity of 100%for 48 hours allowing ideal conditions for fungal invasion to occur. Theplants are removed to the greenhouse bench and held for 7-10 days afterwhich visual ratings are made. Ratings are by Infection Index (I I)where 0= no infection or 100% control, and 10=100% infection or nocontrol.

To inoculate the plants, a spore suspension of early blight fungus(Alternaria solani) is prepared and sprayed on the plant until itreaches the point of runoff.

The following compounds exhibited foliar fungicidal properties:

4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-one

4,6-dinitro-1,3-benzodithiole-2-one

5-trifluoromethyl-1,3-benzodithiole-2-one

1,3-benzodithiole-2-one

6-cyano-4-nitro-1,3-benzodithiole-2-one

EXAMPLE XIII

For determination of acaricidal activity for the herein disclosedcompounds, the following screening procedure was used: To evaluate acompound as a contact acaricide, the solution is sprayed at 15 psi ontothe leaves of bean seedlings infested with mites as a 0.1%concentration. The sprayed plants are inoculated 24 hours later. In thecase of systemic testing, the chemical is added to the nutrient solutionin which the bean seedling is growing at a concentration of 20 ppm.After three days, mites are added to the leaves grown in the treatedsolution. In both cases, five days later counts are made and percentkill determined.

Two spotted spider mites (Tetranychus urticae) are used in these testsand pinto beans (Phaseolus vulgaris) in the cotylendonary stage is thehost plant species used.

The following compounds exhibited acaricidal properties:

4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-one

4,6-dinitro-1,3-benzodithiole-2-one

6-methyl-4-nitro-1,3-benzodithiole-2-one

4-nitro-1,3-benzodithiole-2-one

6-fluoro-4-nitro-1,3-benzodithiole-2-one

7-chloro-4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-one

7-di-n-propylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

7-monoisopropylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

7-monopropylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

7-diethylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

7-methylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

7-mono-n-butylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

7-diallylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

6-nitro-7-n-propylthio-4-trifluoromethyl-1,3-benzodithiole-2-one

7-isopropylthio-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-thione

5-nitro-1,3-benzodithiole-2-one

5-trifluoromethyl-1,3-benzodithiole-2-one

1,3-benzodithiole-2-thione.

EXAMPLE XIV

For determination of nematocidal activity for the herein disclosedcompounds, the following screening procedure was used: The roots ofestablished tomato plants, grown in the presence of root knot(Meloidogyne incognita) nematodes and with adequately galled roots, arecut into small sgements. The root segments are added to sterile soil andthoroughly mixed. The root knot infested soil is allowed to set forthree days. During this period many larva will emerge from the decayingplant roots yielding a high potential of root knot inoculum soil. Aquantity of the soil mixture is added to 8 oz. cups. Finally, 10 mls ofthe candiate nematocide at 20 ppm is added to the infested soil andthoroughly blended. The treated soil is removed from the jar and placedin an 8 oz. cup. The treated soil is allowed to aerate for 48 hours.Finally, cucumber seeds are planted in the treated soil. After 3-4weeks, evaluations are made based on the galls occurring on thedevelopng cucumber seedlings. The system used is the Root-Knot Index(RKI) based on a 0-10 rating where 0=No galls and 10=100% galling.

The following compounds exhibited nematocidal properties:

4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-one

4,6-dinitro-1,3-benzodithiole-3-one

6-methyl-4-nitro-1,3-benzodithiole-2-one

4-nitro-1,3-benzodithiole-2-one

6-fluoro-4-nitro-1,3-benzodithiole-2-one

5-nitro-1,3-benzodithiole-2-one.

EXAMPLE XV

For determination of insecticidal activity for the herein disclosedcompounds, the following screening procedure was used:

A. Screwworm Test

The candidate compound was evaluated as an insecticide on screwworms atrates of 0.3125-10.0%. The solutions were applied on 1st, 2nd, and 3rdinstar larvi and on eggs.

Two reps of each larvi instar and the eggs were placed on black filterpaper in petri dishes and sprayed with 5 ml total volume at eachconcentration. Rations were made 48 hours following application.

B. White Fly Test

White fly infested tobacco (Nicotiana) plants were sprayed with a 1%solution of candidate test compound. Within 12 hours after applicationof the chemical, all white flies were either dead or had left thetobacco plants. White fly populations were too large to makequantitative counts, so visual observations were made.

The following compound exhibited insecticidal properties in A and Babove:

4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-one

C. Pea Aphid Test

The candidate compounds were applied in a 0.5% solution to pea aphidsand pea seedling plants in a contact test using a Waters vertical spraytower. The spray descends through an 8 inch stainless steel cylinder tothe test insects and plants 44 inches below the atomizer. The spraytower is operated at 10 p.s.i. and discharges about 30 milliliters ofspray per minute through a Devilbiss atomizer. The insects and seedlingswere sprayed for a 15 second period and held for forty-eight hourmortality determinations.

D. Southern Armyworm Test

Excised lima bean leaves were dipped into 0.05% solutions of thecandidate compounds and when dry were offered to 10 larvae of theSouthern armyworm (late third instar) for a 48 hour feeding period.

The following compounds exhibited insecticidal properties in C and Dabove:

4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-one

6-fluoro-4-nitro-1,3-benzodithiole-2-one

7-chloro-4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-one

6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one

It should be understood by those skilled in the art that variousmodifications may be made in the present invention without departingfrom the spirit and scope thereof as described in the specification anddefined in the appended claims.

What is claimed is:
 1. A process for preparing compounds of the formula:##STR5## wherein Y is selected from hydrogen, cyano, alkylsulfonyl,nitro and trifluoromethyl; X is selected from alkyl and alkenyl of up to6 carbon atoms, nitro, trichloromethyl, trifluoromethyl,trifluoromethoxy, trifluoromethylthio, trifluoromethylsulfoxyl,trifluoromethylsulfonyl, methoxymethyl, cyano, carboxy, carbamyl,halogen, hydroxy, acetylamino, amino, N-phenylamino, N,N-diallylamino,alkoxy, N-morpholino, N-piperidino, N-piperazino, N-pyrrolidino,dimethylaminodithiocarbamyl, carboalkoxy, alkylthio, mono- anddialkylamino, N-alkylcarbamyl, N,N-dialkylcarbamyl, alkylsulfoxy,alkylsulfonyl, said alkyl groups containing from 1 to 4 carbon atoms andn is an integer from 0 to 3 which comprises reacting a nitrobenzene ofthe formula: ##STR6## wherein Z is halogen, Y, X and n are as definedabove; with an N,N-dialkyldithiocarbamic acid or acid salt thereof, saidalkyl group containing from 1 to 4 carbon atoms, straight- orbranched-chained, and recovering product.
 2. The process of claim 1wherein said reaction is carried out in the presence of a solvent. 3.The process of claim 1 wherein said reaction is carried out at atemperature of from 0° C. to 200° C.
 4. The process of claim 1 whereinsaid acid salt of N,N-dialkyldithiocarbamic acid is an alkali metalsalt.
 5. The process of claim 4 wherein said alkali metal is sodium. 6.The process of claim 1 wherein said N,N-dialkyldithiocarbamic acid saltis N,N-dimethyldithiocarbamic acid sodium salt.
 7. The process of claim1 for preparing a compound having formula I wherein Y is nitro and n isO which comprises reacting a nitrohalobenzene of formula II wherein Y isnitro and n is O with said N,N-dialkyldithiocarbamic acid or acid saltthereof and recovering product.
 8. The process of claim 7 for preparing4-nitro-1,3-benzodithiole-2-one wherein 2,6-dinitrochlorobenzene isreacted with N,N-dimethyldithiocarbamic acid sodium salt dihydrate. 9.The process of claim 1 for preparing compounds having formula I whereinY is nitro and n is 1 which comprises reacting a nitrohalobenzene offormula II wherein Y is nitro and n is 1 with saidN,N-dialkyldithiocarbamic acid or acid salt thereof and recoveringproduct.
 10. The process of claim 9 for preparing6-methyl-4-nitro-1,3-benzodithiole-2-one wherein2,6-dinitro-4-methylchlorobenzene is reacted withN,N-dimethyldithiocarbamic acid sodium salt dihydrate.
 11. The processof claim 9 for preparing4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-one wherein2,6-dinitro-4-trifluoromethylchlorobenzene is reacted withN,N-dimethyldithiocarbamic acid sodium salt dihydrate.
 12. The processof claim 9 for preparing 4,6-dinitro-1,3-benzodithiole-2-one wherein2,4,6-trinitrochlorobenzene is reacted with saidN,N-dialkyldithiocarbamic acid or acid salt thereof and recoveringproduct.
 13. The process of claim 9 for preparing6-fluoro-4-nitro-1,3-benzodithiole-2-one wherein2,6-dinitro-4-fluorochlorobenzene is reacted with saidN,N-dialkyldithiocarbamic acid or acid salt thereof and recoveringproduct.
 14. The process of claim 9 for preparing6-chloro-4-nitro-1,3-benzodithiole-2-one wherein4-chloro-2,6-dinitrochlorobenzene is reacted with saidN,N-dialkyldithiocarbamic acid or acid salt thereof and recoveringproduct.
 15. The process of claim 9 for preparing6-cyano-4-nitro-1,3-benzodithiole-2-one wherein2,6-dinitro-4-cyanochlorobenzene is reacted with saidN,N-dialkyldithiocarbamic acid or acid salt thereof and recoveringproduct.
 16. The process of claim 1 for preparing compounds havingformula I wherein Y is nitro and n is 2 which comprises reacting anitrobenzene of formula II wherein Y is nitro and n is 2 with saidN,N-dialkyldithiocarbamic acid or acid salt thereof and recoveringproduct.
 17. The process of claim 16 for preparing6-chloro-7-methyl-4-nitro-1,3-benzodithiole-2-one wherein4-chloro-2,6-dinitro-3-methylchlorobenzene is reacted with saidN,N-dialkyldithiocarbamic acid or acid salt thereof and recoveringproduct.
 18. The process of claim 16 for preparing7-chloro-4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-one wherein3-chloro-2,6-dinitro-4-trifluoromethylchlorobenzene is reacted with saidN,N-dialkyldithiocarbamic acid or acid salt thereof and recoveringproduct.
 19. The process of claim 16 for preparing7-dimethylaminodithiocarbamyl-4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-onewherein 3-chloro-2,6-dinitro-4-trifluoromethylchlorobenzene is reactedwith N,N-dimethyldithiocarbamic acid or acid salt thereof and recoveringproduct.
 20. The process of claim 1 for preparing compounds havingformula I wherein Y is nitro and n is 3 which comprises reacting anitrobenzene of formula II wherein Y is nitro and n is 3 with saidN,N-dialkyldithiocarbamic acid or acid salt thereof and recoveringproduct.
 21. The process of claim 20 for preparing5,7-dimethyl-4,6-dinitro-1,3-benzodithiole-2-one wherein3,5-dimethyl-2,4,6-trinitrochlorobenzene is reacted with saidN,N-dialkyldithiocarbamic acid or acid salt thereof and recoveringproduct.
 22. The process of claim 1 for preparing compounds havingformula I wherein Y is trifluoromethyl and n is 1 which comprisesreacting a nitrobenzene of formula II wherein Y is trifluoromethyl and nis 1 with said N,N-dialkyldithiocarbamic acid or acid salt thereof andrecovering product.
 23. The process of claim 22 for preparing6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one wherein2,4-dinitro-6-trifluoromethylchlorobenzene is reacted with saidN,N-dialkyldithiocarbamic acid or acid salt thereof and recoveringproduct.
 24. The process of claim 1 for preparing compounds havingformula I wherein Y is trifluoromethyl and n is 2 which comprisesreacting a nitrobenzene of formula II wherein Y is trifluoromethyl and nis 2 with said N,N-dialkyldithiocarbamic acid or acid salt thereof andrecovering product.
 25. The process of claim 24 for preparing7-di-n-propylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-onewherein 3-di-n-propylamino-2,4-dinitro-6-trifluoromethylchlorobenzene isreacted with said N,N-dialkyldithiocarbamic acid or acid salt thereofand recovering product.
 26. The process of claim 24 for preparing7-monoisopropylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-onewherein 2,4-dinitro-3-monoisopropylamino-6-trifluoromethylchlorobenzeneis reacted with said N,N-dialkyldithiocarbamic acid or acid salt thereofand recovering product.
 27. The process of claim 24 for preparing7-monopropylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-onewherein 2,4-dinitro-3-mono-n-propylamino-6-trifluoromethylchlorobenzeneis reacted with said N,N-dialkylthiocarbamic acid or acid salt thereofand recovering product.
 28. The process of claim 24 for preparing7-diethylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one wherein3-diethylamino-2,4-dinitro-6-trifluoromethylchlorobenzene is reactedwith said N,N-dialkyldithiocarbamic acid or acid salt thereof andrecovering product.
 29. The process of claim 24 for preparing6-nitro-7-n-propylthio-4-trifluoromethyl-1,3-benzodithiole-2-one wherein2,4-dinitro-3-n-propylthio-6-trifluoromethylchlorobenzene is reactedwith said N,N-dialkyldithiocarbamic acid or acid salt thereof andrecovering product.
 30. The process of claim 24 for preparing7-isopropylthio-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-onewherein 2,4-dinitro-3-isopropylthio-6-trifluoromethylchlorobenzene isreacted with said N,N-dialkyldithiocarbamic acid or acid salt thereofand recovering product.
 31. The process of claim 24 for preparing7-diallylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one wherein3-diallylamino-2,4-dinitro-6-trifluoromethylchlorobenzene is reactedwith said N,N-dialkyldithiocarbamic acid or acid salt thereof andrecovering product.
 32. The process of claim 24 for preparing7-methylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one wherein2,4-dinitro-3-methylamino-6-trifluoromethylchlorobenzene is reacted withsaid N,N-dialkyldithiocarbamic acid or acid salt thereof and recoveringproduct.
 33. The process of claim 24 for preparing7-mono-n-butylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-onewherein 2,4-dinitro-3-mono-n-butylamino-6-trifluoromethylchlorobenzeneis reacted with said N,N-dialkyldithiocarbamic acid or acid salt thereofand recovering product.
 34. The process of claim 24 for preparing7-dibutylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one wherein3-dibutylamino-2,4-dinitro-6-trifluoromethylchlorobenzene is reactedwith said N,N-dialkyldithiocarbamic acid or acid salt thereof andrecovering product.
 35. The process of claim 24 for preparing7-monophenylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2onewherein 2,4-dinitro-3-monophenylamino-6-trifluoromethylchlorobenzene isreacted with said N,N-dialkyldithiocarbamic acid or acid salt thereofand recovering product.
 36. The process of claim 24 for preparing6-nitro-7-piperidino-4-trifluoromethyl-1,3-benzodithiole-2-one wherein2,4-dinitro-3-piperidino-6-trifluoromethylchlorobenzene is reacted withsaid N,N-dialkyldithiocarbamic acid or acid salt thereof and recoveringproduct.
 37. The process of claim 24 for preparing7-morpholino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-one wherein2,4-dinitro-3-morpholino-6-trifluoromethylchlorobenzene is reacted withsaid N,N-dialkyldithiocarbamic acid or acid salt thereof and recoveringproduct.
 38. The process of claim 24 for preparing6-nitro-7-pyrrolidino-4-trifluoromethyl-1,3-benzodithiole-2-one wherein2,4-dinitro-3-pyrrolidino-6-trifluoromethylchlorobenzene is reacted withsaid N,N-dialkyldithiocarbamic acid or acid salt thereof and recoveringproduct.
 39. The process of claim 1 for preparing compounds havingformula I wherein Y is hydrogen and n is 1 which comprises reacting anitrobenzene of formula II wherein Y is hydrogen and n is 1 with saidN,N-dialkyldithiocarbamic acid or acid salt thereof and recoveringproduct.
 40. The process of claim 39 for preparing5-trifluoromethyl-1,3-benzodithiole-2-one wherein2-nitro-4-trifluoromethylchlorobenzene is reacted with saidN,N-dialkyldithiocarbamic acid or acid salt thereof and recoveringproduct.
 41. The process of claim 39 for preparing5-nitro-1,3-benzodithiole-2-one wherein 2,4-dinitrochlorobenzene isreacted with said N,N-dialkyldithiocarbamic acid or acid salt thereofand recovering product.
 42. The process according to claim 1 whereinco-produced material separated from compound I by solvent differentialis converted to compound I by treatment under basic conditions andproduct recovered.
 43. The process of claim 42 wherein said treatment iseffectuated with sodium hydroxide in the presence of aqueousdimethylsulfoxide at room temperature and product subsequentlyrecovered.